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1. All gases consist of molecules which are considered as rigid, perfectly elastic, solid spheres. These
molecules are extremely small i.e., the volume occupied by the molecules of the gas is taken negligible
as compared to the volume of the containing vessel.
2. The molecules are in a continuous random motion. They are moving in all directions with all possible
velocities. There is no particular direction of motion of the particles.
3. The molecules during their motion collide with one another and also with the walls of the vessel. At
each collision, their velocities change both in magnitude and direction; however in the steady state,
molecular density remains uniform throughout the gas and does not change with time.
4. No forces of attraction or repulsion are exerted on a gas molecule by other molecules or by the
container except during collisions. This means, the energy of the gas is purely kinetic.
5. The collisions among the molecules or with the walls of container are purely elastic. A collision is said
to perfectly elastic if the energy of the molecules remains same before and after the collision.
6. Molecules travel in a straight line with a uniform velocity in between the collisions. The average distance
travelled by the molecules between the successive collisions is called as mean-free path of a molecule.
The time spent during a collision is assumed to be negligibly small as compared with the time taken by
the molecule in traversing a mean-free path.
Note : A gas which satisfies all of above set of assumptions of kinetic theory of gases under all conditions of
temperature and pressure is called as an ideal gas or perfect gas.
A real gas shows appreciable deviations from the perfect gas. At low temperature and high pressure, gases
show deviation from the ideal behaviour.
Evidences In Support of Molecular Motion
Diffusion :
The phenomenon of diffusion presents a remarkable evidence of molecular motion of matter. The particles
of one substance diffuse into another against gravity due to the molecular motion. H2 diffuses into CO2 when
a jar filled with H2 is held mouth to mouth over a jar filled with CO2, though H2 is lighter than CO2.
Evaporation :
The phenomenon of evaporation is related with the motion of molecules. The molecules of liquid are quite
free to move about. At any temperature, all the molecules dont move with the same velocity, some move
faster than the others. Evaporation involves the escape of fast moving molecules (having speed greater than
average speed). This results in lowering of average speed, which in turn results in lowering of temperature,
and thus producing a cooling effect.
Brownian Motion :
Botanist Robert Brown observed the irregular motion of plane spores floating in water. Such motions are
called as Brownian Motion. Here the motion of each particle is due to inequality of the impact of surrounding
molecules on it. For example: motion of smoke particles in air is a case of Brownian motion. This
supports the view that the molecules of a substance are in constant motion.
1 m0 N 2 1 2 m N
P crms or P crms where = density of gas = 0
3 V 3 V
Root Mean Square Velocity (crms)
crms can be calculated with any of the following results.
3P 3 RT 3kT
crms =
M m0
For the same gas at two different temperatures T1 and T2, crms will be different.
crms 1 T
1 (as Crms T)
crms 2 T2
8RT
cav =
pM
Equipartition of Energy
The Law of equipartition of energy states that for a dynamical system in thermal equilibrium, the total energy
of the system is equally divided amongst the various degrees of freedom.
The share of each degree of freedom is 1/2 kT.
Illustration - 1 Calculate the root mean square speed of argon atoms at room temperature (25C). At
what temperature will the root mean square speed will be half that value ?
SOLUTION :
MAr = 0.040 Kg and R = 8.3 J/mol/K Crms 1 T
1
Crms 2 T2
3 RT 3 8.3 273 25
Crms =
M 0.040 1 T1
= 430.7 m/s 2 298
Illustration - 2 Calculate the pressure of Hydrogen in a cylinder of capacity 10 lt given that the total
kinetic energy of translation is 7.5 103 J. What is the total kinetic energy of molecules in the cylinder ?
(1 atm pressure = 105 N/m2)
SOLUTION :
The total KE of translation in n moles for a P = 5 105 N/m2
diatomic gas is : 5
Total KE for diatomic gas = PV
3 3 2
nRT PV
2 2 5
KE = 5 105 10 103 J
3 2
Hence 7.5 103 J = P (10 103m3 )
2 = 12500 J
Illustration - 3 An Oxygen storage tank has a capacity of 0.05 m3. The gas pressure is 100 atm. at 27C.
Determine :
(a) the total KE of translation of molecules, (b) the average KE of translation of molecules and
(c) the total KE.
SOLUTION :
(a) Total KE of translation = 3/2 PV (c) The total KE (for diatomic gas) = 5/2 nRT
5 5
= 3/2 (100) x 10 x 0.05 = 7.5 10 J = 5/2 PV
(b) Average KE = 3/2 kT = 3/2 (1.38 1023) KE = 5/2 (100) 105 (0.05)
(300) = 6.21 1021 J = 1.25 106 J.
Illustration - 4 Find the number of Hydrogen molecules in 1 cm3 if the pressure is 200 mm Hg and the root
mean square velocity of hydrogen is 2400 m/s in these conditions.
SOLUTION :
200 1 m0 N 2
P = 200 mm Hg 1.01 105 N/M2 Substituting these values P crms
760 3 V
3 PV
V = 1 cm3 = 106 m3 N
2
m0 crms
M
m0 = N N0 = 6.023 1023 200 1.01 105 1 10 6 6.023 10 23
0 N 3
760 0.002 2400 2400
= 4.17 1018 molecules.
Illustration - 5 What is the energy of the rotational motion of the molecules contained in 1 Kg of nitrogen
at a temperature of 7C ?
SOLUTION : 2
n = moles = 1000/28 Rotational Energy = nRT
2
T = 273 + 7 = 280 K
1000
For a diatomic gas, 2 degrees of freedom are for = 8.3 280 J = 8.3 104 J
28
rotational motion.
Illustration - 6 A vessel A with a capacity of V1 = 3 lt contains gas at a pressure of P1 = 2 atm and a vessel
B with a capacity of V2 = 4 lt contains the same gas at a pressure of 1 atm. The temperature is 0C in A and
27C in B. What will be the pressure in the vessels if they are connected by a tube ?
SOLUTION :
The vessels are initially at temperatures : where x = 3 or 5 according to whether the gas
T1 = 273 K and T2 = 300 K is monoatomic and diatomic.
T = final temperature = 283.2K
Let n1 and n2 be the moles in A and B respectively.
n1 n2 RT
Initial total energy = Final total energy Final pressure = P =
V1 V2
x x x
n1 RT 1 n 2 RT 2 n1 n 2 RT 6 4 283.2
2 2 2 P = 1.43 atm.
272 300 7
Note : It may be useful to remember the following :
PV P V nT n T
P 1 1 2 2 and T= 11 2 2
V1 V2 n1 n2
Charles Law :
At a constant pressure the volume of a given quantity of any gas varies directly with the absolute temperature.
V T (for given n and P)
V/T = constant
If V1 and V2 are volumes of a gas at T1 and T2 and the pressure is kept constant, then:
V1 V2
T1 T2
Avogadro Law :
It states that equal volumes of all gases at the same temperature and pressure contain equal numbers of
molecules.
If volume V1 of one gas contains N1 molecules and volume V2 of another gas contains N2 molecules at same
pressure and temperature conditions, then:
V1 V2
N1 N2
Daltons Law of partial pressures :
The total pressure of a mixture of non-reacting gases is equal to the sum of partial pressures of each gas. The
partial pressure of a gas is defined as the pressure it would exert if it were alone in the container at same
temperature.
If PT is the total pressure, p1, p2, p3, ......... are the partial pressures of a number of gases in the container,
then according to Daltons Law of partial pressures:
PT = p1 + p2 + p3 + ...........
If n1, n2, n3, be the respective number of moles of the gases :
RT
PT n1 2 .....
V
SOLUTION :
nRT1 10 0.0821 283 mass 10
(a) V1 = 2.42 L (c) density = d1 = = 4.13 g/L
P1 32 3 V1 2.42
Illustration - 8 A vertical cylinderical tank 1 m high has its top end closed by a tightly fitted frictionless
piston of negligible weight. The air inside the cylinder is at an absolute pressure of 1 atm. The piston is
depressed by pouring mercury on it very slowly. How far will the piston descend before mercury spills over the
top of cylinder ? The temperature of the air inside the cylinder is maintained constant.
SOLUTION :
P1 = initial air pressure = 1 atm = 76 cm Hg
P2 = final air pressure = (76 + x) cm Hg
V1 = initial volume = 100 A
V2 = final volume = (100 x) A
76 (100 A) = (76 + x) (100 x)A
Let A = area of cross-section of cylinder.
7600 = 7600 76x + 100x x2
As the temperature is constant, x = 24 cm
Use P1 V1 = P2 V2 for air inside the cylinder. The piston descends by 24 cm.
Illustration - 9 An air bubble is released from the bottom of a lake at a depth of 11 m. The temperature at
the bottom is 4C and that at the surface is 12C. What is the ratio of the bubbles radius at the surface to its
radius at bottom ? Assume density of water = 1000 Kg/m3, atmospheric pressure = 75 cm of Hg and density
of mercury = 13600 Kg/m3.
SOLUTION :
Let P1 = pressure at the bottom of lake P1 = 75 + 80.88 = 155.88 cm Hg.
= P2 (pressure at surface)
PV PV
+ P (due to water column) Using 1 1 2 2 for the air inside the bubble
T1 T2
Taking cm of Hg as the unit of pressure,
where V1,V2, are the bottom and surface ;
P1 = 75 cm Hg
T1 and T2 are temperatures at bottom and surface
Pressure of water column of height h = h rw g
155.88 V1 75V2
P = Hwg
273 4 273 12
h h
P w ( ) g w cm of Hg. V2 r2 1/ 3
Hg Hg Hg 2.138, 2.138 1.288
V1 r1
1100 1
= cm Hg = 80.88 cm Hg
13.6
SOLUTION :
The pressure, temperature and number of moles n1 RT1
volume of vessel = V
of oxygen in the vessel change due to leak while P1
the volume remains fixed.
Hence using PV = nRT
mass leaking out = 1 n2 (32)
we have : = 1 2/3
P1 P = 1/3 gm.
2
n1T1 n2T2
1 0.082 320
320 5 1 1 V = 0.082 L
n2 moles 32 10
300 8 32 48
Illustration - 11 A bulb of 500 cm3 is joined by a narrow tube of another bulb B of 250 cm3 and the whole
system is initially filled with air at S.T.P. and sealed. If the temperature of the bulb A is now raised to 100C
and that of B is kept constant, find :
(a) the new pressure in the system.
(b) mass of air which is transferred from one bulb to another during heating.
(density of air at S.T.P. = 1.29 g/l)
SOLUTION :
(a) Let P be the final pressure of air in the bulbs. As the bulbs are connected, pressure will be equal in both bulbs.
Let TA and TB be the final temperatures of the bulbs.
TA = 373 K, TB = 273 K
Illustration - 12 A thin tube sealed at both ends, is 100 cm long. It lies horizontally, the middle 0.1 m
containing mercury and the two ends containing air at standard atmospheric pressure. If the tube is turned to
a vertical position, by what amount will the mercury be displaced ?
SOLUTION :
Let P0, V0 be the pressure and volume of the air columns initially.
Let P1, P2 be the final pressures in cm of Hg and V1, V2 be the final volumes.
Applying Boyles Law on both air columns, we get :
P0 V0 = P1 V1 and P0 V0 = P2 V2
PV P (45)
P1 0 0 0
V1 45 x
PV P (45)
and P2 0 0 0
V2 45 x
Substituting to get :
45 P0 45 P0
+ 10 =
45 + x 45 x
THERMODYNAMICS Section - 3
Temperature :
It may be defined as that thermal property which attains the same value for all bodies placed in thermal
contact with each other.
Heat Energy :
The transfer or flow of internal energy caused by the difference of temperatures between two bodies is
called as Heat Energy.
Zeroth Law of thermodynamics :
It two bodies A and B are in thermal equilibrium with another body C, then they are also in thermal equilibrium
with each other.
Thermodynamical system :
It is a collection of an extremely large numbers of atoms or molecules so that they together have some
pressure (P), volume (V) and temperature (T). Examples: a gas, vapour, steam, vapour in contact with the
liquid.
W = PdV
W = PV for constant pressure and we also have W = PV2 PV1 = nRT2 nRT1
W = nRT for constant pressure
The systems state at any instant of time can be specified by two variables (P, V). The relation between
pressure P and volume V can be studied on a pressure - volume (P-V) graph known as indicator diagram or
a P-V diagram.
On such a graph, each equilibrium state of a thermodynamical system can be represented by a point whose
x-coordinate represents volume (V) and y-coordinate represents pressure (P).
A process can be represented by a curve on the P-V diagram. If the gas goes from initial state A (P1,V1) to
the final state B (P2, V2), the work done W is given by :
W = area under the curve AB above the X-axis (shaded portion)
Internal Energy
Internal energy (U) of a system is the total of all kinds of energy
possessed by the atoms and other particles that comprise the system.
The change in internal energy U depends only on the temperature
difference of initial and final states and not on the process between the
states.
In Thermodynamics :
1. Work done by a system is taken as positive (+). Work done on the system is taken as
negative ().
2. Heat gained by a system is taken as positive (+) and the heat lost by the system is taken as
negative ().
3. Increase in internal energy is taken as positive (+) and decrease in internal energy is taken as
negative ().
When we heat the gas at constant volume, the heat is supplied to raise the temperature of gas only. When we
heat the gas at constant pressure, the volume of the gas apart from temperature of the gas rises. When the
gas expands, it does some external work for increasing the volume. So in this case, the heat is supplied :
(a) to raise the temperature of the gas (b) to do the mechanical work for expansion
As a result more amount of heat is required to increase the temperature of the gas through the same amount
when the pressure is kept constant. Hence Cp is always greater than the value of Cv.
Cp Cp
The ratio of is denoted by i.e. = ( >1)
Cv Cv
3 3 3
Cv = V = R T 1 RT R
2 2 2
3 5 Cp 5
Cv = R and Cp = R (as Cp Cv = R)
2 2 Cv 3
7 Cp 7
Cp = R (as Cp Cv = R) =
2 Cv 2
Illustration - 13 One mole of oxygen is heated at constant pressure from 0C. What must be the quantity of
heat that should be supplied to the gas for the temperature to be doubled ? If the same heat is supplied to the
gas at constant volume, what will be the final temperature ?
SOLUTION :
T 1 = 0 + 273 = 273 K = 7930.6 J
Temperature is to be doubled If heating is done at constant volume :
T 2 = 2T1 = 546 K Q = n Cv T
Q at constant pressure = n Cp T nR
Q = 1 T
7
Hence Q = n Cp T = n R T
2 1 8. 3
7 7930.6 = 1.4 1 (273)
Q = 1 8.3 (546 273)
2 T = 655 K
Illustration - 14 When water is boiled under a pressure of 2 atm., the heat of vapourisation is 2.20 106
J/Kg and the boiling point is 120C. At this pressure 1 Kg of water has a volume of 103 m3 and 1 Kg of
steam has a volume of 0.824 m3.
(a) Compute the work done when 1 Kg of steam is formed at this temperature.
(b) Compute the increase in the internal energy.
SOLUTION :
(a) Work done = P (V) (at constant pressure) (b) U = Q W
W = 2 atm (0.824 0.001) m3 U = m L W
W = 2 1.013 105 N/m2 0.823 m3 U = 1 kg 2.20 106 J/kg 166.74 kJ
= 166.74 kJ = (2200 166.74) = 2033.26 kJ
SOLUTION :
(a) At constant volume : (b) At constant pressure :
W =0 Q = m Cp T = 3000 0.0595 100
Q = m Cv T = 3000 0.0357 100 ; = 17.85 kcal
T = 80 (20) = 100C W = P (V2 V1) = nR (T2 T1)
SOLUTION :
Path i a f
Q = 50 cal ; W = 20 cal
U = Q W
U = 50 20 = 30 cal
Uf Ui = 30 cal.
As internal energy change is a State function, U will be same for any path from i to f.
(a) Path i b f
W = Q U
W = 36 (Uf Ui) = 36 (30) = 6 cal
(b) Path f i
Q = U + W = (Ui Uf) + W
= (30) + (13) = 43 cal.
(c) Uf Ui = 30 cal
Uf = Ui + 30 = 40 cal
(d) Process i b
Q = U + W
Q = (Ub Ui) + (W)ibf
{(W)ib = (W)ibf because (W)bf = 0}
Q = (22 10) + 6 = 18 cal
(d) Process b f
Q = U + W
Q = (Uf Ub) + 0 = 40 22 = 18 cal.
Isothermal process :
An isothermal process is one in which the temperature remains constant.
A gas under going an isothermal process should remain in perfect thermal contact with a constant temperature
heat reservoir. The gas obeys Boyles Law, during an isothermal process, i.e. PV = constant
As the temperature remains constant internal energy of the system remains constant.
i.e., U = 0 (for isothermal process)
From Ist Law : Q = W
Adiabatic process :
In an adiabatic process, no heat enters or leaves the
system. Such a situation is achieved by heavily insulating
the system.
From Ist Law of thermodynamics : Q = U + W
In adiabatic process Q = 0
U+W=0
The gas in this process obeys the relation :
PV = constant ( = Cp /Cv)
P1V1 = P2V2
Note : The adiabatic curve in P-V diagram is much steeper than the isothermal curve.
Isochoric process :
A process in which the volume remains constant is known
as isochoric process.
For an isochoric process, an ideal gas is taken in a container
with rigid walls so that neither expansion nor compression occurs.
The gas obeys the relation : P T
In isochoric process, W = 0. So from Ist Law of
thermodynamics : Q = U.
(a) If heat is given to the gas, its temperature and pressure rise.
Its internal energy also rises. U and Q are both positive.
(b) If heat is taken out from the gas, its temperature and pressure fall.
Its internal energy also decreases. Q and U are both negative.
Isobaric process :
A process in which the pressure is kept constant is called as isobaric
process.
For isobaric process, the external pressure on the piston is kept
constant.
The gas obeys Charles Law : V T
The work done : W = P (V2 V1)
= n R (T2 T1)
V2 V
Isothermal Process : W 2.303 nRT log10 Q 2.303 nRT og10 2
V1 V1
PV P V nR T1 T2
Adiabatic Process : W 11 2 2 Q = 0
1 1
Adiabatic process :
No heat transfer takes place.
P1 V1 = P2 V2 T1 V1 1 = T2 V2 1 T1 P11 = T2 P21
Illustration - 17 An ideal gas undergoes an isothermal expansion at 0C from 0.010 m3 to 0.200 m3. For 5
moles of gas, compute the work done, the heat added, and the change in internal energy.
SOLUTION :
Let V1 = 0.01 m3 ; V2 = 0.2 m3 ;
T1 = T2 = 273 K ; n = 5 moles
V2
W = 2.303 nRT1 log 10 V
1
W = 2.303 5 8.3 273 log10 20 = 33.946 J.
As U = 0 for isothermal process, Q = W = 33946 J.
Illustration - 18 A gasoline engine takes in 5 moles of air at 20C and 1 atm., and compresses it adiabatically
to 1/10th of the original volume. Find the final temperature and pressure. Assume air to be diatomic. Also
find the work done and change in internal energy.
SOLUTION :
Let P1 = 1 atm. n = 5 moles T1 = 293 K
V2 = V1/10
Using P1 V1 = P2 V2
1
V1
P2 = P1 = 1 (10)1.4 = 25.12 atm.
V2
= 25.12 atm.
Using T1V1 1 = T2V2 1
1
V1
T2 = T1 = 293(10)0.4 = 736 K
V2
Illustration - 19 How much work is done by an ideal gas is expanding isothermally from an initial
volume of 3 L at 20 atm to a final volume of 24 L ?
SOLUTION :
In isothermal process at temperature T :
V2
W = 2.303 nRT log10 V
1
V2
W = 2.303 (P1V1) log10 V (using P1V1 = nRT)
1
24
= 2.303 (20 3) log10 L atm.
3
= 2.303 60 log10 8 (101) J
= 1.26 104 J
Illustration - 20 In a cylinder, 2.0 moles of an ideal monoatomic gas initially at 1.0 106 Pa and 300 K
expands until its volume doubles. Compute the work done if the expansion is :
(a) isothermal (b) adiabatic (c) isobaric
SOLUTION :
Let P1 = 1 106 Pa = 106 N/m2 ;
T1 = 300 K ; n = 2 moles
and Final volume = 2 (initial volume)
V2 = 2 V1
SOLUTION :
(a) Process a b is clearly isobaric at P = 4 atm. Process b c :
W = P (Vb Va) = 4 (16.4 8.2) = 32.8L atm Isothermal, T = 0 U = 0
Wa b = 32.8 101 J = 3313 J Process c a : U for complete cyclic process
is zero because it depends on initial and final
Process b c is isothermal (given)
States i.e. temperature difference only.
Vc
W = 2.303 nRT log10 V (U)ab + (U)bc + (U)ca = 0
b
1200 + 0 + (U)ca = 0
Vc
W = 2.303 (Pb Vb) log10 V
b (U)ca = 1200 cal.
8.2 (c) Using first law of thermodynamics:
W = 2.303 (4 16.4 101) log10
16.4 (Q)ab = (U)ab + Wab
Wb c = 4592.5J
= (1200 + 3313/4.18) cal
Process c a is isochoric (volume is constant) = 1992.5 cal
Wc a = 0 J
(Q)ab = 1992.5 cal
(b) Process a b (Q)bc = (U)bc + Wbc
U = n Cv T = (0 4592.5/4.18) cal = 1098.7 cal
PbVb PaVa (Q)bc = 1098.7 cal.
U = nCv PV = nRT
nR nR (Q)ca = (U)ca + Wca
Cv 3 = 1200 + 0 = 1200 cal
= PbVb PaVa
R 0.0821 Q = 1200 cal.
(4 16.4 4 8.2) = 1200 cal.
SOLUTION :
(a) The process ab is adiabatic because it steeper
than ac.
(b) Pa = 16 atm Vb = 4 L Va = 1 L Ta = 600K
Process ab (adiabatic)
Pa Va = Pb Vb
1.5
V 1
Pb Pa a 16
Vb 4
Pb = 2 atm.
As bc is isobaric, Pb = Pc = 2 atm.
(c) Tc = Ta = 600K because ac is isothermal.
Process ab (adiabatic)
Tb can be calculated using Ta Va 1 = Tb Vb 1
PaVa PbVb
or
Ta Tb
1 0.5
Hence Tb = Ta Va 1
600 300 K
Vb 4
Illustration - 23 6 grams of hydrogen gas at a temperature of 273K were isothermally expanded to five
times its initial volume and then isochorically heated so that the pressure in the final state becomes equal
to that in the initial state. Find the total amount of heat absorbed by the gas during the entire process.
SOLUTION :
Represent the processes on the PV diagram by the curve 1 to 2 (isothermal) and the line 2 to 3 (isochoric).
P1 = P3
For the process 1 to 2 (isothermal)
T2 = T1 = 273 ; V2 = 5 V1
Q = U + W = 0 + W
V2
Q = 2.303 nRT1 log10
V1
6
Q = 2.303 8.3 273 log10 5
2
= 10942.4 J
State 1 and state 3 are at the same pressure.
V1 V3 V3
T3 = V T1 = 5 273 = 1365 K
T1 T3 1
Process 2 to 3 (isochoric)
Q = U + W
Q = n Cv T + 0
6 5
Q = R T3 T2
2 2
Q = 7.5 8.3 (1365 273) J = 67977 J
Illustration - 24 One mole of a perfect gas, initially at a pressure and temperature of 105 N/m2 and 300K
respectively expands isothermally until its volume is doubled and then adiabatically until its volume is again
doubled. Find the final pressure and temperature of the gas. Find the total work done during the isothermal
and adiabatic processes.
Given = 1.4. Also draw the P-V diagram for the process.
SOLUTION :
Let (P1 V1 T1) be the initial pressure, volume and
the temperature of the gas.
For isothermal expansion (1 to 2)
We have : V2 = 2V1
Using, P1 V1 = P2 V2
P2 = P1(V1/V2) = P1/2 = 0.5 105 N/m2.
and T2 = T1 = 300 K
For adiabatic expansion (2 to 3) Hence final pressure and temperatures are
Using P2 V2 = P3 V3 and V3 = 2 V2 1.9 104 N/m2 and 227.35 K
Work Done :
V2
P3 = P2 = 0.5 105 (0.5)1.4 W = W1 2 + W2 3
V3 W = 2.303 nRT1
4 2
= 1.9 10 N/m V2 nR T2 T3
1 1 log10
Also, T2 V2 = T3 V3 V1 1
-1 0.4 W = R (2.303 300 log10 2) +
v2 1
T3 = T 2 = 300 = 227.35 K
v3 4 R 300 227.35
= 3233.56 J
0.4
Example - 1 A flask of volume 2l, provided with a stopcock contains oxygen at 300 K and atmospheric
pressure. The system is heated to a temperature of 400 K, with the stopcock open to the atmosphere. The
stopcock is then closed and the flask is then cooled to its original temperature.
(a) What is the final pressure of oxygen in the flask ? (b) How many grams of oxygen remain in the
flask ?
SOLUTION :
P 3
P3 at 300 atm.
400 4
Loss of grams of O2 = (n1 n2) 32
3
= n1 n1 32 = 8n1
4
P V 8 1 2
= 8 at = 0.6504 gm
RT1 0.082 300
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Example - 2 A tube closed at one end contains a mercury column 15 cm long inside it. The length of air
column trapped between the closed end and mercury is 40 cm when the tube is horizontal. Find the length of
air column if:
(a) the tube is made vertical with open end downwards.
(b) the tube is kept inclined at 60 with the vertical with open end downwards.(Patm = 75 cm Hg)
SOLUTION :
Let A be the crosssectional area and x be the length of Hg column. Let P1, P2 be the pressures in air column
in the vertical and inclined positions respectively.
Let y1, y2 be the lengths of the corresponding air columns.
Applying Boyles Law : P0 V0 = P1 V1 = P2 V2
Where P0 = atm. pressure,
V0 = 40 A, V1 = y1 A, V2 = y2 A
Balancing forces on Hg columns :
P1 + x = P and P2 + x cos 60 = P0
P0 V0 = P1 V1
75 (40 A) = (75 15) y1
y1 = 50 cm.
P0 V0 = P2 V2
75 (40 A) = (75 15 cos 60) (y2 A)
y2 = 44. 4 cm
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Example - 3 An open glass tube is immersed in Hg in such a way that a length of 8 cm extends above
the Hg level. The open end of the tube is then closed and the tube is raised vertically up by 44 cm. What
will be the length of the air column above Hg in the tube now ?
SOLUTION :
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Gaseous State and Thermodynamics Vidyamandir Classes
SOLUTION :
Let P1 and P2 be the initial and final pressures in the air column above Hg inside the tube. Let x be the height
of Hg column after the tube has been raised.
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Example - 5 A cylinder fitted with a movable piston contains hydrogen at a pressure of 3.5 105 N/m2
and a temperature 366 K. Hydrogen expands adiabatically until the pressure in the cylinder falls to 0.7 105
N/m2. The piston is then fixed and the gas is heated until the temperature becomes 366 K. The pressure in the
cylinder is now found to be 1.1 105 N/m2. Determine the molar specific heats of hydrogen.
SOLUTION :
Represent the processes on P-V diagram by curve
1 to 2 (adiabatic) and the line 2 to 3 (isochoric).
Hence P1 = 3.5 105 N/m2
P2 = 0.7 105 N/m2
T1 = 366 K T2 = ?
5 2
P3 = 1.1 10 N/m T3 = 366 K
Process 2 to 3 (isochoric)
P2 P3
T = T
2 3
P2 0.7
T2 = P T3 1.1 366 232.90 K
3
Process 1 to 2 (adiabatic)
T1 P11 = T2 P21
T1 1 1 11
1
1
T2 5 7 5
R R
Thus Cp = = 29.58 J mol1 K1 and Cv = = 21.28 J mol1 K1
1 1
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Example - 6 The rectangular box shown in fig. has a partition which can slide without friction along
the length of the box. Initially each of two chambers of the box has one mole of a monoatomic ideal gas ( =
5/3) at a pressure of P0, volume V0 and temperature T0. The chamber on the left is slowly heated by an electric
heater. The walls of box and partition are thermally insulated. Heat loss through lead wires of heater is
negligible. The gas in the left chamber expands by pushing the partition until the final pressure in both
chambers becomes (243/32) P0. Determine :
(a) the final temperature of the gas in each chamber, (b) the work done by the gas in the right
chamber.
1/ 3/ 5
P0 32 8V
V1 V0 V0 0
P1 243 27
SOLUTION :
and T0 V0 1 = T1 V1 1
Let P1, V1, T1 and P2, V2, T2 be the final pressure,
1 2/3
volume, temperature in the right and left chambers V 27 9
respectively. T1 T0 0 T0 T0
V1 8 4
It is very important to observe that P1 = P2
because the partition is in equilibrium and V1 + In left chamber :
V2 = 2V0 because total volume remains same. 8 46
We have : V2 = 2V0 V1 = 2V0 V0 V0
The process in the left chamber is none of the 27 27
PV P0V0 P2V2
four standard processes, so we will use =
T T0 T2
constant.
P2V2 243 46 207
The process in the right chamber is adiabatic. T2 = T0 T0 V0
P0V0 32 27 27
243
We have P1 = P2 P 207 9
32 0 Hence the final temperatures are T0 and T0
16 4
Work done :
Considering adiabatic compression in right
chamber :
P0V0 PV
1 1
W=
1
In right chamber :
P0V0 243 8 15
We have : P0 V0 = P1 V1 W= 1 P0 V0
1 32 27 8
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Example - 8 Two moles of an ideal monatomic gas, initially at pressure p1 and volume V1, undergo an
adiabatic compression until its volume is V2. Then the gas is given heat Q at constant volume V2.
(a) Sketch the complete process on a P-V diagram
(b) Find the total work done by the gas, the total change in its internal energy and the final temperature of
the gas.
[Give your answers in terms of P1, V1, V2, Q and R.]
SOLUTION :
(a) Figure displays the PV diagram of the gas Work done by the gas on heating at
undergone the given two processes. constant volume
Since the volume is held constant
W2 = 0
The total work done by the gas is
2/ 3
3 P1 V1 V1
W = W1 + W2 1
2 V2
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V 2/ 3
3 P1 V1 Q = CV T = CV (T3 T2)
1 1
3 V2 2/3
2 n R Q Q PV V
2 T3 = T2 1 1 1
CV n R n R V2
P1 V1 V 2 / 3
1 1 Since n = 2 mol, we get :
T2 = n R V2
2/3
Q p V V1
T3 1 1
Change in temperature on heating the gas 3R 2R V2
SOLUTION :
In the process AB, we will have The negative sign implies that the work is done
on the gas.
PV = nRT and PT = K . . . . (i)
(b) The change in energy of the gas in the process
nRT 2 AB is
Eliminating P, we get : V
K
3
U AB n CV T 2 R T1 2T2
dV 2nRT 2
. . . . (ii)
dT K
= 900 R
(a) The expression of work done by the gas is :
Now from the first law of thermodynamics,
W P dV QAB = UAB + WAB = 1200 R 900 R
TB = 2100 R
K 2nRT
W dT The negative sign implies that the heat is released
TA
T K
in the process AB. The process BC takes place
[Using Equations (i) and (ii)] at constant pressure. Hence
T1 WBC = P V = (2P1) (VC VB)
WAB 2nR dT nRT1 nRT1
2T1 = 2 P1 P 2 P
1 1
= 2 nT1R
= nRT1
= 2 2 (300 K) R = 1200 R
= 2 300 R = 600 R
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Now, V
W AC nRT ln A
3 VC
U BC n CV 2 R TC TB
2 (where T = 2T1)
= 3 (R) (2T1 T1) = 3(R) 300 = 900 R = 2 R 2 300 log10 2
= 1200 R log10 2
The positive sign implies that the heat is absorbed
in the process BC. UCA = 0
The process CA takes place at constant QCA = UCA + WCA
temperature. Hence = 0 + 1200 R log10 2
Example - 10 A cubical box of side 1 metre contains helium gas (atomic weight 4) at a pressure of 100
2
N/s . During an observation time of 1 second, an atom travelling with the root-mean-square speed parallel
to one of the edges of the cube, was found to make 500 hits with a particular wall, without any collision
25
with other atoms.Take R J/mol-Kand
3
k = 1.38 1023 JK.
(a) Evaluate the temperature of the gas. (b) Evaluate the average kinetic energy per atom.
(c) Evaluate the total mass of helium gas in the box.
SOLUTION :
(a) We have : 1000 2 4 103 kg mol 1 160 K
Distance travelled by the atom in successive hit
to one of the edges of the cube is l = 2m
3 25 / 3 J 1 mol 1
Number of hits with the wall in one second is (b) The average kinetic energy per atom is
N = 500/s
3 3
KE kT 1.38 1023 J K 1 160 K
2 2
= 3.31 1021 J
(c) Using the expression
m
PV nRT RT
Hence, distance travelled in one second, i.e. root M
mean square speed of atom, is PVM
We get : m
Vrms = l N = (2 m) (500/s) = 1000 m/s RT
Since the root mean square speed of gaseous 100 Pa 1 m3 4 103 kg mol 1
atoms is given by vrms 3 RT / M , we get :
v2 M
25 / 3 J K 1 mol 1 160 K
T rms = 3.0 104 kg
3R
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THINGS TO REMEMBER
1. (a) If the molecules are moving speeds c1, c2, c3, ................., cN ;
then the root mean square speed of the gas is defined as :
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5. Internal Energy
Internal energy (U) of a system is the total of all kinds of energy possessed by the atoms and other particles
that comprise the system. The change in internal energy U depends only on the temperature difference of
initial and final states and not on the process between the states.
U = Uf Ui
6. First Law of Thermodynamics
heat energy given increase in work done
to the system internal energy by the system
Q = U + W.
Cp 5
Cv 3
7 Cp 5
Cp = R
2 Cv 3
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Isobaric process :
1 V2 V
Pressure remains constant. V T T T
2 2
Adiabatic process :
No heat transfer takes place.
P1 V1 = P2 V2 T1 V1 1 = T2 V2 1 T1 P11 = T2 P21
V2 V2
Isothermal Process : W 2.303 nRT log10 Q 2.303 nRT og10
V1 V1
PV P V nR T1 T2
Adiabatic Process : W 11 2 2 Q = 0
1 1
W = nR (T2 T1)
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My Chapter Notes
Illustration - 1